WO2005094584A1

WO2005094584A1 - 5,6-cycloalkyl-7-aminotriazolopyrimidines, method for production and use thereof for the prevention of fungal pests and agents comprising the same

Info

Publication number: WO2005094584A1
Application number: PCT/EP2005/003216
Authority: WO
Inventors: Jordi Tormo I Blasco; Carsten Blettner; Bernd Müller; Markus Gewehr; Wassilios Grammenos; Thomas Grote; Joachim Rheinheimer; Peter Schäfer; Frank Schieweck; Anja Schwögler; Oliver Wagner; Matthias NIEDENBRÜCK; Maria Scherer; Siegfried Strathmann; Ulrich Schöfl; Reinhard Stierl
Original assignee: Basf Aktiengesellschaft
Priority date: 2004-03-30
Filing date: 2005-03-26
Publication date: 2005-10-13
Also published as: BRPI0508976A; TW200601973A; AR050144A1; UY28831A1; US20080058208A1; PE20060020A1; IL177657A0; CN1937921A; EP1734825A1; JP2007530619A

Abstract

The invention relates to 5,6-cycloalkyl-7-aminotriazolopyrimidines of formula (I), where X = alkylene or alkenylene, whereby the carbon chain can be interrupted by one or two heteroatoms selected from S, O or NR1, R1 = H, alkyl or C(=O)-alkyl, L = halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, alkinyl or NR2R3; R2,R3 = each one of the groups given for R1 and m = a whole number from 0 to 5, whereby the aliphatic groups can be substituted by one to three of the following groups: halogen, cyano, nitro, hydroxy, alkoxy, alkylthio, or NRaRb, where Ra, Rb = H or alkyl in which the carbon chains can be halogenated. The invention further relates to methods for production of said compounds, agents comprising the same and use thereof for the prevention of fungal pests harmful to plants.

Description

5,6-Cycloalkyl-7-amino-tria2θlopyrimidines, process 2U of their preparation and their use for controlling harmful fungi and agents containing them

description

The present invention relates to 5,6-cycloalkyl-7-amino-tria2θlopyrimidines of the formula

in the

X C ₁ -C ₂ -alkylene or C ₂ -C ₁₂ -alkenylene, where the carbon chains may be interrupted by one or ₂ heteroatoms selected from S, Q or NR ¹ ,

R ^{1 is} hydrogen, CC ₆ alkyl or C (= O) -CC ₆ alkyl;

L is halogen, cyano, nitro, CC ₁₂ -AlkyI, Cι C ₂ -haloalkyl, CrC ₁₂ alkoxy, CrC ₁₂ - haloalkoxy, Cι-C ₁₂ -alkenyl, CC ^ alkynyl or NR ² R ^3;

R ² , R ^{3 are} each one of the groups mentioned in R ¹ ; and

m is a gan2e number from 0 to 5;

wherein the aliphatic groups may be substituted by one to three of the following groups.

Halogen, cyano, nitro, hydroxy, CC ₆ -alkoxy, CC ₆ -alkylthio, NR ^a R ^b ;

R ^a , R ^{b are} hydrogen or CC ₆ alkyl; wherein the carbon chains may in turn be halogenated;

In addition, the invention relates to the process for the preparation of these compounds, to compositions containing them and to their use for the control of phytopathogenic harmful fungi.

In GB 1 148 629 5,6-dialkyl-7-amino-triazolopyrimidines are generally proposed. EP-A 141 317 discloses individual fungicidally active 5,6-dialkyl-7-amino-triazolopyrimidines. However, their effect is in many cases unsatisfactory. Based on this, the object of the present invention is to provide gene with improved effect and / or broadened spectrum of activity.

Accordingly, the compounds defined above were found. Furthermore, processes and intermediates for their preparation, agents containing them and methods for controlling harmful fungi using the compounds l were found.

The compounds of the formula I differ from those of the abovementioned publications by the cyclic group X.

The compounds of the formula I have an over the known compounds increased activity against harmful fungi.

The compounds of the invention can be obtained in various ways. Advantageously, the compounds according to the invention are obtained by reacting substituted β-ketoesters of the formula II with 3-amino-1,2,4-triazole of the formula III to give 7-hydroxytriazolopyrimidines of the formula IV. The groups L _m and X in formulas II and IV have the meanings as for formula I and the group R in formula II mean C 1 -C ₄ -alkyl, for practical reasons, methyl or ethyl is preferred therein.

III IV

The reaction of the substituted β-keto esters of the formula II with the aminools of the formula III can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble. Alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, amides such as dimethylformamide, diethylformamide, dibutylformamide, NN-dimethylacetamide, lower alkanoic acids such as formic acid, acetic acid, propionic acid or bases such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, in particular alkali metal alkyls, alkyl magnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium, as well as organic bases, for example tertiary amines such as trimethylamine , Triethylamine, triisopropylethylamine, tributylamine and N-methylpiperidine, N-methylmorpholine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and bicyclic amines and mixtures thereof Solvent with water in question. Particularly preferred is the reaction without Solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methylpyrrolidone performed. Particularly preferred bases are tertiary amines such as triisopropylethylamine, tributylamine, N-methylmorpholine or N-methylpiperidine. The temperatures are between 50 and 300 ° C, preferably at 50 to 150 ° C, when working in solution [see. EP-A 770615; Adv. Het. Chem. Vol. 57, p. 81 ff. (1993)].

The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The condensation products of the formula IV thus obtained usually precipitate out of the reaction solutions in pure form and after washing with the same solvent or with water and subsequent drying with halogenating agents, in particular chlorinating or brominating 2U compounds of the formula V, in the Hal is chlorine or bromine, in particular chlorine, reacted.

Preferably, the reaction is carried out with chlorinating agents, such as phosphorus oxychloride, thionyl chloride or sulfuryl chloride at 50 ° C. to 150 ° C., preferably in excess phosphorus oxytrichloride at reflux temperature. After evaporation of the excess Phosphoroxitrichlorids the residue is treated with ice water optionally with the addition of a water-immiscible solvent. The isolated from the dried organic phase optionally after evaporation of the inert solvent chlorination product is usually very pure and is then reacted with ammonia in inert solvents at 100 ° C to 200 ° C to give compounds I. The reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.

The compounds I are optionally isolated after evaporation of the solvent by trituration in water as crystalline compounds.

The β-keto esters of the formula II can be prepared as described in Tetrahedron (2000), Bd.56, p. 2075; Synlett (2001), p. 214 or Can. J. Chem. (1991), p. 853, or are commercially available.

Alternatively, the novel compounds of the formula I can be obtained by reacting substituted compounds of the formula VI, in which L _m and X have the meanings indicated above, with 3-amino-1,2,4-triazole of the formula III.

The reaction can be carried out in the presence or absence of solvents. It is advantageous to use such solvents 2u, to which the ingredients are substantially inert and in which they are gan2 or partially soluble. Alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, amides such as dimethylformamide are particularly suitable as solvents. Diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, acetic acid, propionic acid or bases, as mentioned above, and mixtures of these solvents with water in question. The reaction temperatures are between 50 and 300 ^° C, preferably at 50 to 150 ^° C, when working in solution.

The compounds I are optionally isolated after evaporation of the solvent or dilution with water as crystalline compounds.

The substituted alkyl cyanides of the formula VI required for the preparation of the compounds I are known in some cases or can be prepared by known methods from alkyl cyanides and carboxylic esters with strong bases, 2.B. Alkali hydrides, alkali metal amides or metal alkyls [cf .: J. Am. Chem. Soc. Bd.73, p.3766 (1951)], and alternatively from cyclic ketones via halogenation, in particular α-bromination [cf .: J. Org. Chem. Bd.23, p.1322 (1958)] and substitution with metal cyanides [ See: Chem. Ber., Vol. 44.-S.2067 (1911); Soc. Soc. Chim. Fr., p.1951 (1979); Chem. Soc, Chem. Commun., P.932 (1977), J. Am. Chem. Soc., Vol. 62, p. 359 (1940)].

If any of the compounds I are not accessible in the ways described above, they can be prepared by derivatization of other compounds I.

However, unless isomeric mixtures are involved in the synthesis, separation is not necessarily required because the individual isomers can partially interconvert during processing for use or in use (e.g., under light, acid, or base action). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus to be controlled.

In the definitions of the symbols given in the above formulas, collective terms have been used that are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or mono- or di-branched hydrocarbon radicals having 1 to 4, or 5 to 12 carbon atoms, for example C 1 -C ₆ -alkyl, such as methyl, ethyl, Propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyi, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl , 1, 3-dimethylbutyl, 2,2-diethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2 Trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

Halomethyl: methyl group in which partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl;

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 5 to 12 carbon atoms and one or two double bonds in any position, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl -1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3 -Butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1propenyl, 1-ethyl -2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl _{"2-methyl-1-pentenyl,} 3-methyl-1-pentenyl, 4 -Methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl 3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl , 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1, 2-dimeth yi-2-butenyl, 1, 2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2,2- Dimethyl 3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3- Dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2- propenyl;

Alkynyl: straight-chain or branched hydrocarbon groups having 2 to 7 carbon atoms and one or two triple bonds in any position, for example C ₂ -C ₆ -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl , 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3 Methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2 pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl , 4-methyl-1-pentynediol, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2 -dimethyl-3- butinyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

Cycloalkyl: mono- or bicyclic saturated hydrocarbon groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

Alkylene: divalent straight or branched chains of 1 to 12 CH ₂ groups, eg CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH and CH ₂ CH CH ₂ CH ₂ CH ₂ ;

Alkenylene: divalent unbranched or branched chains of 2 to 12 CH ₂ groups with one or more double bonds at any position, eg CH = CH,

CH ₂ CH = CHCH ₂ CH ₂ , CH = CHCH = CH, CH = CHCH = CHCH ₂ ;

Included within the scope of the present invention are the (R) and (S) isomers and the racemates of compounds of formula I having chiral centers.

With regard to their intended use of the triazolopyrimidines of the formula I, the following meanings of the substituents, in each case alone or in combination, are particularly preferred:

The alkylene groups X in formula I are preferably unbranched or mono- or di-branched, in particular unbranched, alkylene groups.

Another embodiment of the compounds according to the invention relates to those of the formula I, in which X represents an alkylene or alkenylene group, which groups are interrupted by an oxygen or sulfur atom or a group NR ¹ .

R ¹ in formula I is preferably an alkyl group.

The group L is preferably halogen or cyano, particularly preferably NR ² R ³ , where R ^{2 is} preferably alkyl and R ^{3 is} hydrogen or alkyl, more preferably L is alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl and alkynyl.

The index m is preferably zero, 1 or 2.

The aliphatic groups in formula I, if substituted, preferably carry halogen, cyano, alkoxy or alkylthio groups. In addition, preference is given to compounds of the formula I which have a branch in X on a terminal carbon atom, in particular on the atom adjacent to C6.

In addition, compounds I are preferred in which the group X is substituted by a halogen atom or an alkoxy group.

In particular, with regard to their use, the compounds I compiled in the following table are preferred. The groups mentioned in the tables for a substituent also individually, independently of the combination in which they are mentioned, represent a particularly preferred embodiment of the relevant substituent.

# denotes the bond to carbon C6

The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes, in particular from the class of Oomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.

They are particularly important for the control of a large number of fungi on various crops such as \ ne \ zen, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, wine, fruit and vegetables. and ornamental plants and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, as well as the seeds of these plants.

Specifically, they are suitable for controlling the following plant diseases: Alternaria-Aüen on vegetables and fruits, Bipolaris and Drechslera A anen on cereals, rice and grass, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, • Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Fusarium and Verticillium plants on various plants, Mycosphaerella species on cereals, bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, • Podosphaera leucotricha on apples, Pseudocercosporella herpotrichoides on wheat and barley, Pseudoperonospora on hops and cucumbers, Puccinia on cereals, Pyricularia oryzae on rice, Rhizoctonia species on cotton, rice and turf, Septoria tritici and Stagonospora nodorum on wheat, Uncinula necator on vines, Ustilago species on cereals and sugar cane, as well as Venturia species (scab) on apples and pears.

In particular, they are suitable for controlling harmful fungi from the class of Oomycetes, such as Phytophthora infestans, Plasmopara viticola and Pseudoperonospora species.

The compounds I are also suitable for controlling harmful fungi such as Pecilomyces variotii in the protection of materials (2 nd wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.

In the seed treatment, in general, amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of seed are needed.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.

The compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma Butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used, - carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose. The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Examples of formulations are: 1. Products for dilution in water

A Water Soluble Concentrates (SL)

10 parts by weight of a compound of the invention in water or a dissolved water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves.

B Dispersible Concentrates (DC) 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.

C Emulsifiable Concentrates (EC) 15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). Dilution in water results in an emulsion.

D Emulsions (EW, EO) 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E suspensions (SC, OD)

20 parts by weight of a compound according to the invention are comminuted with the addition of dispersants and wetting agents and water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.

F Water-Dispersible and Water-Soluble Granules (WG, SG) 50 parts by weight of a compound according to the invention are finely ground with the addition of dispersing and wetting agents and by means of technical equipment (2.b. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules produced. Dilution in water results in a stable dispersion or solution of the active ingredient.

G Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of dispersants and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. 2. Products for direct application

H dusts (DP)

5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dust.

I Granules (GR, FG, GG, MG)

0.5 parts by weight of a compound according to the invention are finely ground and combined with 95.5% excipients. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.

J ULV solutions (UL)

10 parts by weight of a compound of the invention are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

The concentrations of active substance in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives. To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the inventive compositions in a weight ratio of 1:10 to 10: 1.

The agents according to the invention, in the form of application as fungicides, may also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or with fertilizers. When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity.

The following list of fungicides with which the compounds according to the invention can be used together is intended to illustrate, but not limit, the possible combinations.

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph,

Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil,

• antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, • azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, Myclobutanil, penconazole, propiconazole, prochlorazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimol, triflumizole, triticonazole, dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,

Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb,

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboximine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazoi, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, picobenzamide, probenazole, proquinazide, pyrifenox, Pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforine,

Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate, nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalic-isopropyl,

Phenylpyrroles such as fenpiclonil or fludioxonil, Sulfur, other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorotrilone, cyflufenamid, cymoxanil, dazomet, diclomethine, diclocymet, diethofen-carb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl , Fosetyl-aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide, strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxime-methyl, metominostrobin, orysastrobin, Picoxystrobin, pyraclostrobin or trifloxystrobin, sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid, cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.

synthesis Examples

The instructions given in the Synthesis Examples below were used with appropriate modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the following table with physical data.

Example: Preparation of 5,6,7,8-tetrahydro [1,2,4] triazolo [5,1-b] quinazolin-9-ylamine [I-2]

A mixture of 1, 27 mol of 2-cyano-cyclohexanone and 3-amino-1, 2,4-triazole and 0.25 mol of p-toluenesulfonic acid in 900 ml of mesitylene was heated to 170 ° C for about 4 hrs. After cooling to about 20 to 25 ° C, the precipitate was filtered off and dissolved in dichloromethane. The organic phase was washed with water, then dried and freed from the solvent. There remained 113 g of the title compound. Table I - Compounds of the formula I

Examples of the effect against harmful fungi

The active ingredients were formulated separately as stock solution with a concentration of 10,000 ppm in DMSO. The active compounds were diluted with water according to the concentration indicated.

Use Example 1 - Activity against Pythium species in the microtiter test.

50 μl of the required active substance concentration were pipetted into a microtiter plate (MTP). Subsequently, the inoculation was carried out with 50 μl of an aqueous zoospore suspension of Pythium species. The plates were placed in a steam-saturated chamber at temperatures of 18 ° C. With a photometer, the absorbance of the MTPs was measured on the seventh day after inoculation at 405 nm. Measured parameters were compared to drug-free control growth (100% growth) and blank to determine the relative% growth of pathogens in each agent.

In this assay, the relative growth of the 125 ppm compound I-2-treated pathogens was 7% of the untreated control.

Use Example 2 Activity against the causative agent of the late blight Phytophthora infestans in the microtiter test.

50 μl of the required active substance concentration were pipetted into a microtiter plate (MTP). Subsequently, the inoculation was carried out with 50 .mu.l of an aqueous Sporangien- flooding of Phytophthora infestans. The plates were placed in a steam-saturated chamber at temperatures of 18 ° C. With a photometer, the absorbance of the MTPs was measured on the seventh day after inoculation at 405 nm. Measured parameters were compared to drug-free control growth (100% growth) and blank to determine the relative% growth of pathogens in each agent.

in this assay, the relative growth of the 125 ppm compound I-2-treated pathogens was 6% of the untreated control.

Claims

claims

1. 5,6-Cycloalkyl-7-amino-triazolopyrimidines of the formula I.

in the

X CrCι ₂ alkylene or C ₂ alkenylene -Cι _2, wherein the carbon chains with one or two heteroatoms selected from S, O or NR ¹ can be interrupted,

R is hydrogen, C -, - C ₆ alkyl or C (= O) -C ₁ -C ₆ alkyl;

L is halogen, cyano, nitro, C Cι ₂ alkyl, -C ₂ haloalkyl, dC ^ alkoxy, C haloalkoxy d, CC ₁₂ -alkenyl, CC ₁₂ -alkynyl or NR ² R ^3;

R ² , R ^{3 are} each one of the groups mentioned in R ¹ ; and an integer of 0 to 5; wherein the aliphatic groups may be substituted by one to three of the following groups.

Halogen, cyano, nitro, hydroxy, C 1 -C ₆ alkoxy, C 1 -C ₆ alkylthio, NR ^a R ^b ; R ^a , R ^{b are} hydrogen or d-Ce-alkyl; wherein the carbon chains may in turn be halogenated.

2. A process for the preparation of compounds of the formula I according to claim 1, which comprises reacting β-ketoesters of the formula II,

in which R is CC ₄ alkyl, with 3-amino-1, 2,4-triazole of the formula

to 7-hydroxytriazolopyrimidines of the formula IV

which converts to compounds of the formula V,

in which shark is chlorine or bromine, halogenated, and V is reacted with ammonia.

3. Process for the preparation of compounds of the formula I according to Claim 1, characterized in that compounds of the formula VI

with 3-amino-1, 2,4-tria2θl of formula III according to claim 2.

4. Compounds of formula IV and V according to claim 2.

5. A fungicidal composition containing a solid or liquid carrier and a compound of the formula I according to claim 1

6. Seed containing 1 to 1000 g of a compound of formula I according to claim 1 per 100 kg.

7. A method for controlling phytopathogenic harmful fungi, characterized in that the fungi, or to be protected against fungal attack materials, plants, the soil or seeds treated with an effective amount of a compound of formula I according to claim 1.